Internal donor structure for olefin polymerization catalysts and methods of making and using same

ABSTRACT

The presently disclosed and claimed inventive concept(s) relates to solid catalyst components comprising titanium, magnesium, halogen and an internal electron donor compound having at least one ester group and at least one alkoxy group, and catalyst systems containing the catalyst solid components, organoaluminum compounds, and organosilicon compounds. The presently disclosed and claimed inventive concept(s) further relates to methods of making the catalyst components and the catalyst systems, and methods of polymerizing or copolymerizing alpha-olefins using the catalyst systems.

TECHNICAL FIELD

The presently disclosed and claimed inventive concept(s) relatesgenerally to solid catalyst components for olefin polymerization. Inparticular, the solid catalyst components comprise titanium, magnesium,halogen and internal electron donor compounds containing at least oneester group and at least one alkoxy group. The presently disclosed andclaimed inventive concept(s) further relates to catalyst systemscontaining the solid catalyst components, methods of making the solidcatalyst components and the catalyst systems, and methods ofpolymerizing or copolymerizing alpha-olefins using the catalyst systems.

BACKGROUND

Polyolefins are a class of polymers derived from simple olefins. Knownmethods of making polyolefins involve the use of Ziegler-Nattapolymerization catalysts. These catalysts polymerize vinyl monomersusing a transition metal halide to provide a polymer with an isotacticstereochemical configuration.

Two types of Ziegler-Natta catalyst systems are traditionally used forthe polymerization or copolymerization of olefins. The first, in itsbroadest definition, comprises TiCl₃ based catalysts componentsobtained, for example, by the reduction of TiCl₄ with Al-alkyls, used incombination with Al-compounds such as diethylaluminum chloride (DEAC).Despite the modest properties of the resulting polymers in terms ofisotacticity, the catalysts are characterized by a very low activitywhich results in the presence of large amounts of catalytic residues inthe polymers.

The second type of catalyst system comprises a solid catalyst component,constituted by magnesium dihalide on which are supported a titaniumcompound and an internal electron donor compound. In order to maintainthe high selectivity for an isotactic polymer product, a variety ofinternal electron donor compounds must be added during the catalystsynthesis. Conventionally, when a higher crystallinity of the polymer isrequired, an external donor compound is also added during thepolymerization reaction. Both the internal and external electron donorcompounds become indispensible compositions of catalyst components.

During the past 30 years, numerous supported Ziegler-Natta catalystshave been developed which afford a much higher activity in olefinpolymerization reactions and significantly higher contents ofcrystalline isotactic fractions in the polymers they produce. With thedevelopment of new internal and external electron donor compounds,polyolefin catalyst systems have been continuously improved.

SUMMARY

The following presents a simplified summary of the presently disclosedand claimed inventive concept(s) in order to provide a basicunderstanding of some aspects of the presently disclosed and claimedinventive concept(s). This summary is not an extensive overview of thepresently disclosed and claimed inventive concept(s). It is intended toneither identify key or critical elements of the presently disclosed andclaimed inventive concept(s) nor delineate the scope of the presentlydisclosed and claimed inventive concept(s). Rather, the purpose of thissummary is to present various concepts of the presently disclosed andclaimed inventive concept(s) in a simplified form as a prelude to themore detailed description that is presented hereafter.

The presently disclosed and claimed inventive concept(s) provides asolid catalyst component for use in olefin polymerization, an olefinpolymerization catalyst system containing the solid catalyst component,methods of making the solid catalyst component and the catalyst system,and methods of polymerizing and/or copolymerizing olefins involving theuse of the catalyst system. The solid catalyst component comprisestitanium, magnesium, halogen, and an internal electron donor compoundcontaining at least one ester group and one alkoxy group. The internalelectron donor compound comprises a compound represented by a generalformula (I):

wherein, R₁ is a cycloaliphatic group comprising from about 3 to about20 carbon atoms, an aryl group comprising from about 6 to about 20carbon atoms, an alkylaryl group comprising from about 7 to about 20carbon atoms, or an arylalkyl group comprising from about 7 to about 20carbon atoms; and R₂ and R₃ are identical or different and are eachindependently a substituted or unsubstituted hydrocarbyl having 1 toabout 20 carbon atoms.

A catalyst systems can contain a solid catalyst component comprisingtitanium, magnesium, halogen and an internal electron donor compoundcontaining at least one ester group and one alkoxy group; anorganoaluminum compound; and an organosilicon compound. The internalelectron donor compound comprises a compound represented by the generalformula (I). A solid catalyst component can be made by contacting amagnesium compound and a titanium compound with an internal electrondonor compound containing at least one ester group and one alkoxy group.The internal electron donor compound can be represented by the generalformula (I). A method of polymerizing or copolymerzing olefins involvecontacting olefins with a catalyst system containing a solid catalystcomponent comprising titanium, magnesium, halogen and an internalelectron donor compound that can be represented by the general formula(I), an organoaluminum compound, and an organosilicon compound.

In order to achieve the foregoing and related ends, the presentlydisclosed and claimed inventive concept(s) involves the featureshereinafter fully described and particularly pointed out in the claims.The following description and the annexed drawings set forth in detailcertain illustrative aspects and implementations of invention. These areindicative, however, of but a few of the various ways in which theprinciples of the presently disclosed and claimed inventive concept(s)may be employed. Other objects, advantages and novel features of thepresently disclosed and claimed inventive concept(s) will becomeapparent from the following detailed description of the presentlydisclosed and claimed inventive concept(s) when considered inconjunction with the drawings and one of ordinary skill in the art wouldappreciate such additional objects, advantages, and novel features givenin the present disclosure.

BRIEF SUMMARY OF THE DRAWINGS

FIG. 1 is a schematic diagram of an olefin polymerization system inaccordance with one aspect of the presently disclosed and claimedinventive concept(s).

FIG. 2 is a schematic diagram of an olefin polymerization reactor inaccordance with one aspect of the presently disclosed and claimedinventive concept(s).

FIG. 3 is a schematic diagram of a system for making impact copolymer inaccordance with one aspect of the presently disclosed and claimedinventive concept(s).

DETAILED DESCRIPTION

The presently disclosed and claimed inventive concept(s) relates tosolid catalyst components containing titanium, magnesium, halogen andinternal electron donor compounds containing at least one ester groupand at least one alkoxy group in olefinic polymerization; olefinpolymerization catalyst systems containing the solid catalystcomponents, organoaluminums, and organosilicons; methods of making thesolid catalyst components and the catalyst systems; and methods ofpolymerizing and/or copolymerizing olefins using the catalyst systems.

An aspect of the presently disclosed and claimed inventive concept(s) isa solid catalyst component comprising titanium, magnesium, halogen andan internal electron donor compound containing at least one ester groupand at least one alkoxy group. In one embodiment, the solid catalystcomponent comprises a titanium compound having at least onetitanium-halogen bond and an internal electron donor compound containingat least one ester group and at least on alkoxy group supported on amagnesium halide crystal lattice. The titanium compound is TiCl₄ orTiCl₃. In one embodiment, the magnesium halide crystal lattice is amagnesium dichloride crystal lattice, which is widely known by one ofordinary skill in the art as a support for Ziegler-Natta catalysts.

The solid catalyst component of the presently disclosed and claimedinventive concept(s) is an active catalyst component comprising areaction product of a titanium compound, a magnesium compound, and aninternal electron donor compound containing at least one ester group andat least one alkoxy group. The titanium compounds used in thepreparation of the solid catalyst component include, for example, atetravalent titanium compound represented by chemical formula (II):Ti(OR)_(g)X_(4-g)  (II)wherein R represents a hydrocarbon group, preferably an alkyl grouphaving 1 to about 20 carbon atoms, X represents a halogen atom, and0≦g≦4. Specific examples of the titanium compound include, but are notlimited to, titanium tetrahalides such as TiCl₄, TiBr₄ and TiI₄;alkoxytitanium trihalides such as Ti(OCH₃)Cl₃, Ti(OC₂H₅)Cl₃,Ti(O-n-C₄H₉)Cl₃, Ti(OC₂H₅)Br₃ and Ti(O-i-C₄H₉)Br₃; dialkoxytitaniumdihalides such as Ti(OCH₃)₂Cl₂, Ti(OC₂H₅)₂Cl₂, Ti(O-n-C₄H₉)₂Cl₂ andTi(OC₂H₅)₂Br₂; trialkoxytitanium monohalides such as Ti(OCH₃)₃Cl,Ti(OC₂H₅)₃Cl, Ti(O-n-C₄H₉)₃Cl and Ti(OC₂H₅)₃Br; and tetraalkoxytitaniumssuch as Ti(OCH₃)₄, Ti(OC₂H₅)₄ and Ti(O-n-C₄H₉)₄. Among these, thehalogen containing titanium compounds, especially titanium tetrahalides,have been found to be useful for at least one embodiment. These titaniumcompounds may be used individually or in solutions of hydrocarboncompounds or halogenated hydrocarbons.

The magnesium compounds used in the preparation of the solid catalystcomponent include halogen containing magnesium compounds. Specificexamples of the magnesium compounds include, but are not limited to,magnesium halides such as magnesium chloride, magnesium bromide,magnesium iodide and magnesium fluoride; alkoxy magnesium halides suchas methoxy magnesium chloride, ethoxy magnesium chloride, isopropoxymagnesium chloride, butoxy magnesium chloride and octoxy magnesiumchloride; aryloxy magnesium halides such as phenoxy magnesium chlorideand methylphenoxy magnesium chloride; alkoxy magnesiums such as ethoxymagnesium, isopropoxy magnesium, butoxy magnesium, n-octoxy magnesiumand 2-ethylhexoxy magnesium; aryloxy magnesiums such as phenoxymagnesium and dimethylphenoxy magnesium; and carboxylic acid salts ofmagnesium such as magnesium laurate and magnesium stearate. Thesemagnesium compounds may be in the liquid or solid state.

In one embodiment, the halogen containing magnesium compounds, such asmagnesium chloride, alkoxy magnesium chlorides and aryloxy magnesiumchlorides, are employed.

When preparing the solid catalyst component, an internal electron donorcan be added to the preparation and/or may form the solid catalystcomponent itself and/or other constituents. The solid titanium catalystcomponent can be made by contacting a magnesium compound and a titaniumcompound with an internal electron donor compound. In one embodiment,the solid titanium catalyst component is made by contacting a magnesiumcompound and a titanium compound in the presence of an internal electrondonor compound. In another embodiment, the solid titanium catalystcomponent is made by forming a magnesium based support optionally withthe titanium compound and optionally with the internal electron donorcompound, and contacting the magnesium based support with the titaniumcompound and the internal electron donor compound.

The internal electron donor compound comprises at least one least oneester group and at least one alkoxy group and can be represented by thefollowing chemical formula

wherein R₁ is a cycloaliphatic group comprising from about 3 to about 20carbon atoms, an aryl group comprising from about 6 to about 20 carbonatoms, an alkylaryl group comprising from about 7 to about 20 carbonatoms, or an arylalkyl group comprising from about 7 to about 10 carbonatoms; and R₂ and R₃ are identical or different and are eachindependently a substituted or unsubstituted hydrocarbyl having 1 toabout 20 carbon atoms.

In one embodiment, R₂ and R₃ are identical or different and each mayindependently be a linear or branched alkyl group comprising from 1 toabout 20 carbon atoms, a cycloaliphatic group comprising from about 3 toabout 20 carbon atoms, an aryl group comprising from about 6 to about 20carbon atoms, an alkylaryl group comprising from about 7 to about 20carbon atoms, or an arylalkyl group comprising from about 7 to about 20carbon atoms.

The internal electron donor compound comprises, in one embodiment, atleast one ester group and at least one alkoxy group and can also berepresented by the following chemical formula (III):

wherein R₁ and R₂ are independently hydrogen, C₁-C₂₀ linear or branchedalkyl, C₃-C₂₀ cycloalkyl, phenyl, C₇-C₁₀ arylalkyl, or C₇-C₁₈ alkylarylgroups; and R₃-R₇ are independently hydrogen, or C₁-C₄ linear orbranched alkyl.

In one embodiment, the internal electron donor compound comprises atleast one selected from the group consisting of 1-alkyl-2-methoxyethylbenzoate, 1-alkyl-2-methoxy ethyl 2-alkylbenzoate,1-alkyl-2-methoxy ethyl 3-alkylbenzoate, 1-alkyl-2-methoxy ethyl4-alkylbenzoate and 1-alkyl-2-methoxy ethyl 3,5-dialkylbenzoate.

Specific examples of the 1-alkyl-2-methoxy ethylbenzoate include, butare not limited to, 1-ethyl-2-methoxy ethylbenzoate, 1-propyl-2-mthoxyethylbenzoate, 1-isopropyl-2mthoxy ethylbenzoate, 1-t-butyl-2-methoxyethylbenzoate, 1-isobutyl-2-mthoxy ethylbenzoate, 1-n-butyl-2-methoxyethylbenzoate, 1-n-pentyl-2-methoxy ethylbenzoate, 1-isopentyl-2-methoxyethylbenzoate, 1-n-hexyl-2-methoxy ethylbenzoate, 1-isohexyl-2-methoxyethylbenzoate, 1-n-heptyl-2-methoxy ethylbenzoate, 1-isoheptyl-2-methoxyethylbenzoate, 1-n-octyl-2-methoxy ethylbenzoate, 1-isooctyl-2-methoxyethylbenzoate, 1-nonyl-2-methoxy ethylbenzoate, and 1-isononyl-2-methoxyethylbenzoate.

Specific examples of the 1-alkyl-2-methoxy ethyl 2-alkylbenzoateinclude, but are not limited to, 1-ethyl-2-methoxy ethyl2-methylbenzoate, 1-ethyl-2-methoxy ethyl 2-ethylbenzoate,1-ethyl-2-methoxy ethyl 2-propylbenzoate, 1-ethyl-2-methoxy ethyl2-butylbenzoate, 1-propyl-2-methoxy ethyl 2-methylbenzoate,1-propyl-2-methoxy ethyl 2-ethylbenzoate, 1-propyl-2-methoxy ethyl2-propylbenzoate, 1-propyl-2-methoxy ethyl 2-butylbenzoate,1-isopropyl-2-methoxy ethyl 2-methylbenzoate, 1-isopropyl-2-methoxyethyl 2-ethylbenzoate, 1-isopropyl-2-methoxy ethyl 2-propyllbenzoate,1-isopropyl-2-methoxy ethyl 2-butylbenzoate, 1-t-butyl-2-methoxy ethyl2-methylbenzoate, 1-t-butyl-2-methoxy ethyl 2-ethylbenzoate,1-t-butyl-2-methoxy ethyl 2-propylbenzoate, 1-t-butyl-2-methoxy ethyl2-butylbenzoate, 1-isobutyl-2-methoxy ethyl 2-methylbenzoate,1-isobutyl-2-methoxy ethyl 2-ethylbenzoate, 1-isobutyl-2-methoxy ethyl2-propylbenzoate, 1-isobutyl-2-methoxy ethyl 2-butylbenzoate,1-n-butyl-2-methoxy ethyl 2-methylbenzoate, 1-n-butyl-2-methoxy ethyl2-ethylbenzoate, 1-n-butyl-2-methoxy ethyl 2-propylbenzoate,1-n-butyl-2-methoxy ethyl 2-butylbenzoate, 1-n-pentyl-2-methoxy ethyl2-methylbenzoate, 1-n-pentyl-2-methoxy ethyl 2-ethylbenzoate,1-n-pentyl-2-methoxy ethyl 2-propylbenzoate, 1-n-pentyl-2-methoxy ethyl2-butylbenzoate, 1-isopentyl-2-methoxy ethyl 2-methylbenzoate,1-isopentyl-2-methoxy ethyl 2-ethylbenzoate, 1-isopentyl-2-methoxy ethyl2-propylbenzoate, 1-isopentyl-2-methoxy ethyl 2-butylbenzoate,1-n-hexyl-2-methoxy ethyl 2-methylbenzoate, 1-n-hexyl-2-methoxy ethyl2-ethylbenzoate, 1-n-hexyl-2-methoxy ethyl 2-propylbenzoate,1-n-hexyl-2-methoxy ethyl 2-butylbenzoate, 1-isohexyl-2-methoxy ethyl2-methylbenzoate, 1-isohexyl-2-methoxy ethyl 2-ethylbenzoate,1-isohexyl-2-methoxy ethyl 2-propylbenzoate, 1-isohexyl-2-methoxy ethyl2-butylbenzoate, 1-n-heptyl-2-methoxy ethyl 2-methylbenzoate,1-n-heptyl-2-methoxy ethyl 2-ethylbenzoate, 1-n-heptyl-2-methoxy ethyl2-propylbenzoate, 1-n-heptyl-2-methoxy ethyl 2-butylbenzoate,1-isoheptyl-2-methoxy ethyl 2-methylbenzoate, 1-isoheptyl-2-methoxyethyl 2-ethylbenzoate, 1-isoheptyl-2-methoxy ethyl 2-propylbenzoate,1-isoheptyl-2-methoxy ethyl 2-butylbenzoate, 1-n-octyl-2-methoxy ethyl2-methylbenzoate, 1-n-octyl-2-methoxy ethyl 2-ethylbenzoate,1-n-octyl-2-methoxy ethyl 2-propylbenzoate, 1-n-octyl-2-methoxy ethyl2-butylbenzoate, 1-isooctyl-2-methoxy ethyl 2-methylbenzoate,1-isooctyl-2-methoxy ethyl 2-ethylbenzoate, 1-isooctyl-2-methoxy ethyl2-propylbenzoate, 1-isooctyl-2-methoxy ethyl 2-butylbenzoate,1-nonyl-2-methoxy ethyl 2-methylbenzoate, 1-nonyl-2-methoxy ethyl2-ethylbenzoate, 1-nonyl-2-methoxy ethyl 2-propylbenzoate,1-nonyl-2-methoxy ethyl 2-butylbenzoate, 1-i-nonyl-2-methoxy ethyl2-methylbenzoate, 1-i-nonyl-2-methoxy ethyl 2-ethylbenzoate,1-i-nonyl-2-methoxy ethyl 2-propylbenzoate, and 1-i-nonyl-2-methoxyethyl 2-butylbenzoate.

Specific examples of the 1-alkyl-2-methoxy ethyl 3-alkylbenzoateinclude, but are not limited to, 1-ethyl-2-methoxy ethyl3-methylbenzoate, 1-ethyl-2-methoxy ethyl 3-ethylbenzoate,1-ethyl-2-methoxy ethyl 3-propylbenzoate, 1-ethyl-2-methoxy ethyl3-butylbenzoate, 1-propyl-2-methoxy ethyl 3-methylbenzoate,1-propyl-2-methoxy ethyl 3-ethylbenzoate, 1-propyl-2-methoxy ethyl3-propylbenzoate, 1-propyl-2-methoxy ethyl 3-butylbenzoate,1-isopropyl-2-methoxy ethyl 3-methylbenzoate, 1-isopropyl-2-methoxyethyl 3-ethylbenzoate, 1-isopropyl-2-methoxy ethyl 3-propyllbenzoate,1-isopropyl-2-methoxy ethyl 3-butylbenzoate, 1-t-butyl-2-methoxy ethyl3-methylbenzoate, 1-t-butyl-2-methoxy ethyl 3-ethylbenzoate,1-t-butyl-2-methoxy ethyl 3-propylbenzoate, 1-t-butyl-2-methoxy ethyl3-butylbenzoate, 1-isobutyl-2-methoxy ethyl 3-methylbenzoate,1-isobutyl-2-methoxy ethyl 3-ethylbenzoate, 1-isobutyl-2-methoxy ethyl3-propylbenzoate, 1-isobutyl-2-methoxy ethyl 3-butylbenzoate,1-n-butyl-2-methoxy ethyl 3-methylbenzoate, 1-n-butyl-2-methoxy ethyl3-ethylbenzoate, 1-n-butyl-2-methoxy ethyl 3-propylbenzoate,1-n-butyl-2-methoxy ethyl 3-butylbenzoate, 1-n-pentyl-2-methoxy ethyl3-methylbenzoate, 1-n-pentyl-2-methoxy ethyl 3-ethylbenzoate,1-n-pentyl-2-methoxy ethyl 3-propylbenzoate, 1-n-pentyl-2-methoxy ethyl3-butylbenzoate, 1-isopentyl-2-methoxy ethyl 3-methylbenzoate,1-isopentyl-2-methoxy ethyl 3-ethylbenzoate, 1-isopentyl-2-methoxy ethyl3-propylbenzoate, 1-isopentyl-2-methoxy ethyl 3-butylbenzoate,1-n-hexyl-2-methoxy ethyl 3-methylbenzoate, 1-n-hexyl-2-methoxy ethyl3-ethylbenzoate, 1-n-hexyl-2-methoxy ethyl 3-propylbenzoate,1-n-hexyl-2-methoxy ethyl 3-butylbenzoate, 1-isohexyl-2-methoxy ethyl3-methylbenzoate, 1-isohexyl-2-methoxy ethyl 3-ethylbenzoate,1-isohexyl-2-methoxy ethyl 3-propylbenzoate, 1-isohexyl-2-methoxy ethyl3-butylbenzoate, 1-n-heptyl-2-methoxy ethyl 3-methylbenzoate,1-n-heptyl-2-methoxy ethyl 3-ethylbenzoate, 1-n-heptyl-2-methoxy ethyl3-propylbenzoate, 1-n-heptyl-2-methoxy ethyl 3-butylbenzoate,1-isoheptyl-2-methoxy ethyl 3-methylbenzoate, 1-isoheptyl-2-methoxyethyl 3-ethylbenzoate, 1-isoheptyl-2-methoxy ethyl 3-propylbenzoate,1-isoheptyl-2-methoxy ethyl 3-butylbenzoate, 1-n-octyl-2-methoxy ethyl3-methylbenzoate, 1-n-octyl-2-methoxy ethyl 3-ethylbenzoate,1-n-octyl-2-methoxy ethyl 3-propylbenzoate, 1-n-octyl-2-methoxy ethyl3-butylbenzoate, 1-isooctyl-2-methoxy ethyl 3-methylbenzoate,1-isooctyl-2-methoxy ethyl 3-ethylbenzoate, 1-isooctyl-2-methoxy ethyl3-propylbenzoate, 1-isooctyl-2-methoxy ethyl 3-butylbenzoate,1-nonyl-2-methoxy ethyl 3-methylbenzoate, 1-nonyl-2-methoxy ethyl3-ethylbenzoate, 1-nonyl-2-methoxy ethyl 3-propylbenzoate,1-nonyl-2-methoxy ethyl 3-butylbenzoate, 1-i-nonyl-2-methoxy ethyl3-methylbenzoate, 1-i-nonyl-2-methoxy ethyl 3-ethylbenzoate,1-i-nonyl-2-methoxy ethyl 3-propylbenzoate, and 1-i-nonyl-2-methoxyethyl 3-butylbenzoate.

Specific examples of the 1-alkyl-2-methoxy ethyl 4-alkylbenzoateinclude, but are not limited to, 1-ethyl-2-methoxy ethyl4-methylbenzoate, 1-ethyl-2-methoxy ethyl 4-ethylbenzoate,1-ethyl-2-methoxy ethyl 4-propylbenzoate, 1-ethyl-2-methoxy ethyl4-butylbenzoate, 1-propyl-2-methoxy ethyl 4-methylbenzoate,1-propyl-2-methoxy ethyl 4-ethylbenzoate, 1-propyl-2-methoxy ethyl4-propylbenzoate, 1-propyl-2-methoxy ethyl 4-butylbenzoate,1-isopropyl-2-methoxy ethyl 4-methylbenzoate, 1-isopropyl-2-methoxyethyl 4-ethylbenzoate, 1-isopropyl-2-methoxy ethyl 4-propyllbenzoate,1-isopropyl-2-methoxy ethyl 4-butylbenzoate, 1-t-butyl-2-methoxy ethyl4-methylbenzoate, 1-t-butyl-2-methoxy ethyl 4-ethylbenzoate,1-t-butyl-2-methoxy ethyl 4-propylbenzoate, 1-t-butyl-2-methoxy ethyl4-butylbenzoate, 1-isobutyl-2-methoxy ethyl 4-methylbenzoate,1-isobutyl-2-methoxy ethyl 4-ethylbenzoate, 1-isobutyl-2-methoxy ethyl4-propylbenzoate, 1-isobutyl-2-methoxy ethyl 4-butylbenzoate,1-n-butyl-2-methoxy ethyl 4-methylbenzoate, 1-n-butyl-2-methoxy ethyl4-ethylbenzoate, 1-n-butyl-2-methoxy ethyl 4-propylbenzoate,1-n-butyl-2-methoxy ethyl 4-butylbenzoate, 1-n-pentyl-2-methoxy ethyl4-methylbenzoate, 1-n-pentyl-2-methoxy ethyl 4-ethylbenzoate,1-n-pentyl-2-methoxy ethyl 4-propylbenzoate, 1-n-pentyl-2-methoxy ethyl4-butylbenzoate, 1-isopentyl-2-methoxy ethyl 4-methylbenzoate,1-isopentyl-2-methoxy ethyl 4-ethylbenzoate, 1-isopentyl-2-methoxy ethyl4-propylbenzoate, 1-isopentyl-2-methoxy ethyl 4-butylbenzoate,1-n-hexyl-2-methoxy ethyl 4-methylbenzoate, 1-n-hexyl-2-methoxy ethyl4-ethylbenzoate, 1-n-hexyl-2-methoxy ethyl 4-propylbenzoate,1-n-hexyl-2-methoxy ethyl 4-butylbenzoate, 1-isohexyl-2-methoxy ethyl4-methylbenzoate, 1-isohexyl-2-methoxy ethyl 4-ethylbenzoate,1-isohexyl-2-methoxy ethyl 4-propylbenzoate, 1-isohexyl-2-methoxy ethyl4-butylbenzoate, 1-n-heptyl-2-methoxy ethyl 4-methylbenzoate,1-n-heptyl-2-methoxy ethyl 4-ethylbenzoate, 1-n-heptyl-2-methoxy ethyl4-propylbenzoate, 1-n-heptyl-2-methoxy ethyl 4-butylbenzoate,1-isoheptyl-2-methoxy ethyl 4-methylbenzoate, 1-isoheptyl-2-methoxyethyl 4-ethylbenzoate, 1-isoheptyl-2-methoxy ethyl 4-propylbenzoate,1-isoheptyl-2-methoxy ethyl 4-butylbenzoate, 1-n-octyl-2-methoxy ethyl4-methylbenzoate, 1-n-octyl-2-methoxy ethyl 4-ethylbenzoate,1-n-octyl-2-methoxy ethyl 4-propylbenzoate, 1-n-octyl-2-methoxy ethyl4-butylbenzoate, 1-isooctyl-2-methoxy ethyl 4-methylbenzoate,1-isooctyl-2-methoxy ethyl 4-ethylbenzoate, 1-isooctyl-2-methoxy ethyl4-propylbenzoate, 1-isooctyl-2-methoxy ethyl 4-butylbenzoate,1-nonyl-2-methoxy ethyl 4-methylbenzoate, 1-nonyl-2-methoxy ethyl4-ethylbenzoate, 1-nonyl-2-methoxy ethyl 4-propylbenzoate,1-nonyl-2-methoxy ethyl 4-butylbenzoate, 1-i-nonyl-2-methoxy ethyl4-methylbenzoate, 1-i-nonyl-2-methoxy ethyl 3-ethylbenzoate,1-i-nonyl-2-methoxy ethyl 4-propylbenzoate, and 1-i-nonyl-2-methoxyethyl 4-butylbenzoate.

Specific examples of the 1-alkyl-2-methoxy ethyl 3,5-dialkylbenzoateinclude, but are not limited to, 1-ethyl-2-methoxy ethyl3,5-dimethylbenzoate, 1-ethyl-2-methoxy ethyl 3,5-diethylbenzoate,1-ethyl-2-methoxy ethyl 3,5-dipropylbenzoate, 1-ethyl-2-methoxy ethyl3,5-dibutylbenzoate, 1-propyl-2-methoxy ethyl 3,5-dimethylbenzoate,1-propyl-2-methoxy ethyl 3,5-diethylbenzoate, 1-propyl-2-methoxy ethyl3,5-dipropylbenzoate, 1-propyl-2-methoxy ethyl 3,5-dibutylbenzoate,1-isopropyl-2-methoxy ethyl 3,5-dimethylbenzoate, 1-isopropyl-2-methoxyethyl 3,5-diethylbenzoate, 1-isopropyl-2-methoxy ethyl3,5-dipropyllbenzoate, 1-isopropyl-2-methoxy ethyl 3,5-dibutylbenzoate,1-t-butyl-2-methoxy ethyl 3,5-dimethylbenzoate, 1-t-butyl-2-methoxyethyl 3,5-diethylbenzoate, 1-t-butyl-2-methoxy ethyl3,5-dipropylbenzoate, 1-t-butyl-2-methoxy ethyl 3,5-dibutylbenzoate,1-isobutyl-2-methoxy ethyl 3,5-dimethylbenzoate, 1-isobutyl-2-methoxyethyl 3,5-diethylbenzoate, 1-isobutyl-2-methoxy ethyl3,5-dipropylbenzoate, 1-isobutyl-2-methoxy ethyl 3,5-dibutylbenzoate,1-n-butyl-2-methoxy ethyl 3,5-dimethylbenzoate, 1-n-butyl-2-methoxyethyl 3,5-diethylbenzoate, 1-n-butyl-2-methoxy ethyl3,5-dipropylbenzoate, 1-n-butyl-2-methoxy ethyl 3,5-dibutylbenzoate,1-n-pentyl-2-methoxy ethyl 3,5-dimethylbenzoate, 1-n-pentyl-2-methoxyethyl 3,5-diethylbenzoate, 1-n-pentyl-2-methoxy ethyl3,5-dipropylbenzoate, 1-n-pentyl-2-methoxy ethyl 3,5-dibutylbenzoate,1-isopentyl-2-methoxy ethyl 3,5-dimethylbenzoate, 1-isopentyl-2-methoxyethyl 3,5-diethylbenzoate, 1-isopentyl-2-methoxy ethyl3,5-dipropylbenzoate, 1-isopentyl-2-methoxy ethyl 3,5-dibutylbenzoate,1-n-hexyl-2-methoxy ethyl 3,5-dimethylbenzoate, 1-n-hexyl-2-methoxyethyl 3,5-diethylbenzoate, 1-n-hexyl-2-methoxy ethyl3,5-dipropylbenzoate, 1-n-hexyl-2-methoxy ethyl 3,5-dibutylbenzoate,1-isohexyl-2-methoxy ethyl 3,5-dimethylbenzoate, 1-isohexyl-2-methoxyethyl 3,5-diethylbenzoate, 1-isohexyl-2-methoxy ethyl3,5-dipropylbenzoate, 1-isohexyl-2-methoxy ethyl 3,5-dibutylbenzoate,1-n-heptyl-2-methoxy ethyl 3,5-dimethylbenzoate, 1-n-heptyl-2-methoxyethyl 3,5-diethylbenzoate, 1-n-heptyl-2-methoxy ethyl3,5-dipropylbenzoate, 1-n-heptyl-2-methoxy ethyl 3,5-dibutylbenzoate,1-isoheptyl-2-methoxy ethyl 3,5-dimethylbenzoate, 1-isoheptyl-2-methoxyethyl 3,5-diethylbenzoate, 1-isoheptyl-2-methoxy ethyl3,5-dipropylbenzoate, 1-isoheptyl-2-methoxy ethyl 3,5-dibutylbenzoate,1-n-octyl-2-methoxy ethyl 3,5-dimethylbenzoate, 1-n-octyl-2-methoxyethyl 3,5-diethylbenzoate, 1-n-octyl-2-methoxy ethyl3,5-dipropylbenzoate, 1-n-octyl-2-methoxy ethyl 3,5-dibutylbenzoate,1-isooctyl-2-methoxy ethyl 3,5-dimethylbenzoate, 1-isooctyl-2-methoxyethyl 3,5-diethylbenzoate, 1-isooctyl-2-methoxy ethyl3,5-dipropylbenzoate, 1-isooctyl-2-methoxy ethyl 3,5-dibutylbenzoate,1-nonyl-2-methoxy ethyl 3,5-dimethylbenzoate, 1-nonyl-2-methoxy ethyl3,5-diethylbenzoate, 1-nonyl-2-methoxy ethyl 3,5-dipropylbenzoate,1-nonyl-2-methoxy ethyl 3,5-dibutylbenzoate, 1-i-nonyl-2-methoxy ethyl3,5-dimethylbenzoate, 1-i-nonyl-2-methoxy ethyl 3,5-diethylbenzoate,1-i-nonyl-2-methoxy ethyl 3,5-dipropylbenzoate, and 1-i-nonyl-2-methoxyethyl 3,5-dibutylbenzoate.

In one embodiment, the solid catalyst component comprises an internalelectron donor compound containing at least one ester group and at leastone alkoxy group, but does not include additional internal electrondonors. In another embodiment, the solid catalyst component includesother internal electron donors in addition to the internal electrondonor compound containing at least one ester group and at least onealkoxy group. For example, when preparing the solid catalyst component,other internal electron donors can be added to the preparation and/ormay form the solid catalyst itself and/or other constituents in additionto the internal electron donor containing at least one ester group andat least one alkoxy group.

Examples of other internal electron donors include oxygen-containingelectron donors such as organic acid esters. Specific examples include,but are not limited to, diethyl ethylmalonate, diethyl propylmalonate,diethyl isopropylmalonate, diethyl butylmalonate, diethyl1,2-cyclohexanedicarboxylate, di-2-ethylhexyl1,2-cyclohexanedicarboxylate, di-2-isononyl1,2-cyclohexanedicarboxylate, methyl benzoate, ethyl benzoate, propylbenzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenylbenzoate, benzyl benzoate, methyl 4-methylbenzoate, ethyl4-methylbenzoate, amyl 4-methylbenzoate, ethyl 4-ethylbenzoate, methylanisate, ethyl anisate, ethyl 4-ethoxybenzoate, diisononyl phthalate,di-2-ethylhexyl phthalate, diethyl succinate, dipropyl succinate,diisopropyl succinate, dibutyl succinate, diisobutyl succinate, dioctylsuccinate, diisononyl succinate, and diether compounds such as9,9-bis(methoxymethyl)fluorine,2-isopropyl-2-isopentyl-1,3-dimethoxypropane,2,2-diisobutyl-1,3-dimethoxypropane,2,2-diisopentyl-1,3-dimethoxypropane,2-isopropyl-2-cyclohexyl-1,3-dimethoxypropane.

The internal electron donor compounds may be used individually or incombination. In employing the internal electron donor compounds, they donot have to be used directly as starting materials, but compoundsconvertible to the electron donors in the course of preparing the solidcatalyst components may also be used as the starting materials.

The solid catalyst component can be made by contacting a magnesiumcompound and a titanium compound with an internal electron donorcompound containing at least one ester group and at least one alkoxygroup.

In one embodiment, the solid catalyst component is made by contacting amagnesium compound and a titanium compound in the presence of aninternal electron donor compound containing at least one ester group andat least one alkoxy group. In another embodiment, the solid catalystcomponent is made by forming a magnesium based support optionally with atitanium compound and optionally with an internal electron donorcompound containing at least one ester group and at least one alkoxygroup, and contacting the magnesium based support with the titaniumcompound and the internal electron donor compound containing at leastone ester group and at least one alkoxy group. In yet anotherembodiment, the solid catalyst component is made by contacting amagnesium based support with a titanium compound to form a mixture, thencontacting the mixture with an internal electron donor compoundcontaining at least one ester group and at least one alkoxy group. Instill yet another embodiment, the solid catalyst component is made bycontacting a magnesium based support with a titanium compound to form amixture, then contacting the mixture with an internal electron compoundcontaining at least one ester group and at least one alkoxy group, thencontacting the mixture again with the internal electron donor compoundcontaining at least one ester group and at least one alkoxy group. Suchrepeated contact with the internal electron donor compound containing atleast one ester group and at least one alkoxy group can occur once,twice, or three times successively or with other acts performed betweencontacts with additional doses of the internal electron donor compoundscontaining at least one ester group and at least one alkoxy group.

Generally, the magnesium based support is made by dissolving a magnesiumcompound in a solvent mixture comprising an organic epoxy compound, anorganic phosphorus compound and an optional inert diluent to form ahomogenous solution.

The organic epoxy compounds used in the presently disclosed and claimedinventive concept(s) include compounds having at least one epoxy groupin the forms of monomers, dimmers, oligomers and polymers. Examples ofepoxy compounds include, but are not limited to aliphatic epoxycompounds, alicyclic epoxy compounds, aromatic epoxy compounds, or thelike. Examples of aliphatic epoxy compounds include, but are not limitedto halogenated aliphatic epoxy compounds, aliphatic epoxy compoundshaving a keto group, aliphatic epoxy compounds having an ether bond,aliphatic epoxy compounds having an ester bond, aliphatic epoxycompounds having a tertiary amino group, aliphatic epoxy compoundshaving a cyano group, or the like. Examples of alicyclic epoxy compoundsinclude, but are not limited to halogenated alicyclic epoxy compounds,alicyclic epoxy compounds having a keto group, alicyclic epoxy compoundshaving an ether bond, alicyclic epoxy compounds having an ester bond,alicyclic epoxy compounds having a tertiary amino group, alicyclic epoxycompounds having a cyano group, or the like. Examples of aromatic epoxycompounds include, but are not limited to halogenated aromatic epoxycompounds, aromatic epoxy compounds having a keto group, aromatic epoxycompounds having an ether bond, aromatic epoxy compounds having an esterbond, aromatic epoxy compounds having a tertiary amino group, aromaticepoxy compounds having a cyano group, or the like.

Specific examples of epoxy compounds include, but are not limited to,epifluorohydrin, epichlorohydrin, epibromohydrin, hexafluoropropyleneoxide, 1,2-epoxy-4-fluorobutane, 1-(2,3-epoxypropyl)-4-fluorobenzene,1-(3,5-epoxybutyl)-2-fluorobenzene, 1-(2,3-epoxypropyl)-4-chlorobenzene,1-(3,5-epoxybutyl)-3-chlorobenzene, or the like. Specific examples ofhalogenated alicyclic epoxy compounds include 4-fluoro-1,2-cyclohexeneoxide, 6-chloro-2,3 epoxybicyclo[2,2,1]heptane, or the like. Specificexamples of halogenated aromatic epoxy compounds include 4-fluorostyreneoxide, 1-(1,2-epoxypropyl)-3-trifluorobenzene, or the like.

The organic phosphorus compounds used in the presently disclosed andclaimed inventive concept(s) include, but are not limited, tohydrocarbyl esters and halohydrocarbyl esters of ortho-phosphoric acidand phosphorous acid. Specific examples include, but are not limited totrimethyl phosphate, triethyl phosphate, tributyl phosphate, triphenylphosphate, trimethyl phosphite, triethyl phosphite, tributyl phosphiteand triphenyl phosphite.

In order to improve the ability of the magnesium compound to bedissolved, an inert diluent may be optionally added to the solventmixture. The inert diluent can typically be aromatic hydrocarbons oralkanes, as long as it is capable of facilitating the dissolution of themagnesium compound. Examples of aromatic hydrocarbons include, but arenot limited to benzene, toluene, xylene, chlorobenzene, dichlorobenzene,trichlorobenzene, chlorotoluene, and derivatives thereof. Examples ofalkanes include linear, branched, or cyclic alkanes having about 3 toabout 30 carbons, such as butane, pentane, hexane, cyclohexane,heptanes, and the like. These inert diluents may be used alone or incombination.

In embodiments of preparing the solid catalyst component according tothe Examples, the magnesium based support is mixed with a titaniumcompound such as liquid titanium tetrahalide to form a solid precipitatein the optional presence of an auxiliary precipitant. The auxiliaryprecipitant may be added before, during or after the precipitation ofthe solids and loaded on the solids.

The auxiliary precipitants used in the presently disclosed and claimedinventive concept(s) include carboxylic acids, carboxylic acidanhydrides, ethers, ketones, or mixture thereof. Specific examplesinclude, but are not limited to, acetic anhydride, phthalic anhydride,succinic anhydride, maleic anhydride, 1,2,4,5-benzene tetracarboxylicdianhydride, acetic acid, propionic acid, butyric acid, acrylic acid,methacrylic acid, acetone, methyl ethyl ketone, benzophenone, dimethylether, diethyl ether, dipropyl ether, dibutyl ether, and dipentyl ether.

Solid precipitation can be carried out by one or more processes selectedfrom the following. One method involves mixing a titanium compound suchas liquid titanium tetrahalide with a magnesium based support at atemperature in the range of about −40 degree Celsius to about 0 degreeCelsius, and precipitating the solids while the temperature is raisedslowly to a range from about 30 degrees Celsius to about 120 degreesCelsius, for example from about 60 degrees Celsius to about 100 degreesCelsius but not by way of limitation. The second method involves addinga titanium compound dropwise into a magnesium based support toprecipitate out solids immediately. The third method involves adding afirst titanium compound dropwise into a magnesium based support andmixing a second titanium compound with the magnesium based support. Inthese methods, an internal electron donor compound containing at leastone ester group and at least one alkoxy group can be present in thereaction system. The internal electron donor compound containing atleast one ester group and at least one alkoxy group can be added eitherafter the magnesium based support is obtained or after the solidprecipitate is formed.

In one embodiment, when the solid catalyst component is formed, asurfactant can be used so as to produce a relatively large size andsubstantially spherical shape of the magnesium based support, therebycontributing to many of the beneficial properties of the solid catalystcomponent and catalyst system. General examples of surfactants includepolymer surfactants, such as polyacrylates, polymethacrylates, polyalkylmethacrylates, and the like. A polyalkyl methacrylate is a polymer thatmay contain one or more methacrylate monomers, such as at least twodifferent methacrylate monomers, at least three different methacrylatemonomers, etc. Moreover, the acrylate and methacrylate polymers maycontain monomers other than acrylate and methacrylate monomers, so longas the polymer surfactant contains at least about 40% by weight acrylateand methacrylate monomers.

In one embodiment, non-ionic surfactants and/or anionic surfactants canbe used. Examples of non-ionic surfactants and/or anionic surfactantsinclude, but are not limited to, phosphate esters, alkyl sulfonates,aryl sulfonates, alkylaryl sulfonates, linear alkyl benzene sulfonates,alkylphenols, ethoxylated alcohols, carboxylic esters, fatty alcohols,fatty esters, fatty aldehydes, fatty ketones, fatty acid nitriles,benzene, naphthalene, anthracene, succinic anhydride, phthalicanhydrides, rosin, terpene, phenol, or the like. In fact, a number ofanhydride surfactants are effective. In some instances, the absence ofan anhydride surfactant causes the formation of very small catalystsupport particles while the over-use creates straw shaped materialsometimes referred to as needles.

The solid catalyst precursor can be formed in one embodiment, asfollows. In a solvent such as toluene, a magnesium and titaniumcontaining solution is seen following the addition of a halogenatingagent such as TiCl₄ into a magnesium based solution at relatively coolertemperatures, such as −25 degrees Celsius until about 0 degrees Celsius.An oil phase is then formed, which can be dispersed into the hydrocarbonphase that is stable until about 40 degrees Celsius. The resultantmagnesium material becomes a semi-solid at this point and the particlemorphology is thereafter determined. The semi-solid product convertsinto a solid between about 40 degrees Celsius and about 80 degreesCelsius.

In order to facilitate obtaining uniform solid particles, the process ofprecipitation can be carried out slowly. When the second method ofadding titanium halide dropwise at low or room temperature is applied,the process may take place over a period from about 1 hour to about 6hours. When the first method of raising the temperature in a slow manneris applied as described hereinafter, the rate of temperature increasecan range from about 4 degrees Celsius to about 125 degrees Celsius perhour.

The solid precipitate is first separated from the mixture. Entrained inthe solid precipitate may be a variety of complexes and byproducts, sothat further treatment may in some instances be necessary as would bewell appreciated and understood by one of ordinary skill in the art. Inone embodiment, the solid precipitate is treated with a titaniumcompound in order to substantially remove the byproducts from the solidprecipitate.

The solid precipitate can be washed with an inert diluent and thentreated with a titanium compound or a mixture of a titanium compound andan inert diluent. The titanium compound used in this treatment can beidentical to or different than the titanium compound used for formingthe solid precipitate. The amount of titanium compound used is fromabout 1 to about 20 moles, such as from about 2 to about 15 moles, permole of magnesium compound in the support. The treatment temperatureranges from about 50 degrees Celsius to about 150 degrees Celsius, suchas from about 60 degrees Celsius to about 100 degrees Celsius. If amixture of titanium tetrahalide and an inert diluent is used to treatthe solid precipitate, the volume % of titanium tetrahalide in thetreating solution is from about 10% to about 100%, the rest being theinert diluent.

The treated solids can be further washed with an inert diluent to removeineffective titanium compounds and other byproducts. The inert diluentherein used can be hexane, heptanes, octane, 1,2-dichloroethane,benzene, toluene, ethylbenzene, xylene, and other hydrocarbons.

By treating the solid precipitate with the titanium compound andoptionally an inert diluent, the byproducts in the solid precipitate canbe removed from the solid precipitate. In one embodiment, the solidprecipitate is treated with the titanium compound and optionally aninert diluent about two times or more and five times or less.

By treating the solid precipitate with an inert diluent, a free titaniumcompound in the solid precipitate can be removed from the solidprecipitate. The resultant solid precipitate does not, in suchcircumstances, substantially contain a free titanium compound. In oneembodiment, the solid precipitate is treated repeatedly with an inertdiluent until the filtrate contains about 100 ppm or less of titanium.In another embodiment, the solid precipitate is treated repeatedly withan inert diluent until the filtrate contains about 50 ppm or less oftitanium. In yet another embodiment, the solid precipitate is treatedwith an inert diluent until the filtrate contains about 10 ppm or lessof titanium. In one embodiment, the solid precipitate is treated with aninert diluent about three times or more and seven times or less. In allcases, one of ordinary skill in the art, given the present disclosure,would be able to vary these parameters and steps in order to tailor thepresently disclosed and claimed inventive concept(s) to specificconditions and/or properties as described.

In one embodiment, the solid catalyst component contains from about 0.5to about 6.0 wt % titanium; from about 10 to about 25 wt % magnesium;from about 40 to about 70 wt % halogen; from about 1 to about 50 wt %the internal electron donor compound containing at least one ester groupand at least one alkoxy group; and optionally inert diluent from about 0to about 15 wt %. In another embodiment, the solid catalyst componentcontains from about 2 to about 25 wt % of one or more of the internalelectron donors containing at least one ester group and at least onealkoxy group. In yet another embodiment, the solid catalyst componentcontains from about 5 to about 20 wt % of one or more of the internalelectron donors containing at least one ester group and at least onealkoxy group.

The amounts of the ingredients used in preparing the solid catalystcomponent may vary depending upon the method of preparation. In oneembodiment, from about 0.01 to about 5 moles of the internal electrondonor compounds containing at least one ester group and at least onealkoxy group and from about 0.01 to about 500 moles of the titaniumcompounds are used per mole of the magnesium compound used to make thesolid catalyst component. In another embodiment, from about 0.05 toabout 2 moles of the internal electron donor compounds containing atleast one ester group and at least one alkoxy group and from about 0.05to about 300 moles of the titanium compounds are used per mole of themagnesium compound used to make the solid catalyst component.

In one embodiment, in the solid catalyst component, the atomic ratio ofhalogen/titanium is from about 4 to about 200; the internal electrondonor/titanium mole ratio is from about 0.01 to about 10; and themagnesium/titanium atomic ratio is from about 1 to about 100. In anotherembodiment, in the solid catalyst component, the atomic ratio ofhalogen/titanium is from about 5 to about 100; the internal electrondonor/titanium mole ratio is from about 0.2 to about 6; and themagnesium/titanium atomic ratio is from about 2 to about 50.

The resulting solid catalyst component generally contains a magnesiumhalide of a smaller crystal size than traditional and/or commerciallyavailable magnesium halides and usually has a specific surface area ofat least about 5 m²/g, such as from about 10 to about 1,000 m²/g, orfrom about 100 to about 800 m²/g. Since the above ingredients areunified to form an integral structure of the solid catalyst component,the composition of the solid catalyst component does not substantiallychange by washing with, for example, hexane.

The solid catalyst component may be used after being diluted with aninorganic or organic compound such as a silicon compound, an aluminumcompound, or the like. One of ordinary skill in the art would appreciatethat while such dilution may be desirable in certain situations it isnot necessary for all applications.

Methods of preparing solid catalyst components, which can be used in thepresently disclosed and claimed inventive concept(s), are described inU.S. Patents and U.S. Patent Publication Nos: U.S. Pat. Nos. 4,771,023;4,784,983; 4,829,038; 4,861,847; 4,990,479; 5,177,043; 5,194,531;5,244,989; 5,438,110; 5,489,634; 5,576,259; 5,767,215; 5,773,537;5,905,050; 6,323,152; 6,437,061; 6,469,112; 6,962,889; 7,135,531;7,153,803; 7,271,119; 2004242406; 20040242407; and 20070021573 which arehereby incorporated by reference in their entirety as those set forthexplicitly therein in this regard.

The catalyst system may contain at least one organoaluminum compound inaddition to the solid catalyst component. Compounds having at least onealuminum-carbon bond in the molecule can be used as the organoaluminumcompound. Examples of organoaluminum compounds include compounds of thefollowing chemical formula (IV):AlR_(n)X_(3-n)  (IV)In formula (IV), R independently represents a hydrocarbon group usuallyhaving 1 to about 20 carbon atoms, X represents a halogen atoms, and0<n≦3.

Specific examples of the organoaluminum compounds represented by formula(IV) include, but are not limited to, trialkyl aluminums such astriethyl aluminum, tributyl aluminum and trihexyl aluminum; trialkenylaluminums such as triisoprenyl aluminum; dialkyl aluminum halides suchas diethyl aluminum chloride, dibutyl aluminum chloride and diethylaluminum bromide; alkyl aluminum sesquihalides such as ethyl aluminumsesquichloride, butyl aluminum sesquichloride and ethyl aluminumsesquibromide; alkyl aluminum dihalides such as ethyl aluminumdichloride, propyl aluminum dichloride and butyl aluminum dibromide;dialkyl aluminum hydrides such as diethyl aluminum hydride and dibutylaluminum hydride; and other partially hydrogenated alkyl aluminum suchas ethyl aluminum dihydride and propyl aluminum dihydride.

The organoaluminum compound is used in such catalyst system of thepresently disclosed and claimed inventive concept(s) in an amount thatthe mole ratio of aluminum to titanium (from the solid catalystcomponent) is from about 5 to about 1,000. In another embodiment, themole ratio of aluminum to titanium in the catalyst system is from about10 to about 700. In yet another embodiment, the mole ratio of aluminumto titanium in the catalyst system is from about 25 to about 400.

The catalyst system may contain at least one organosilicon compound inaddition to the solid catalyst component. This organosilicon compoundmay, although not always, be referred as an external electron donor. Theorganosilicon compound contains silicon having at least one hydrogenligand (hydrocarbon group). General examples of hydrocarbon groupsinclude alkyl groups, cycloalkyl groups, (cycloalkyl)methylene groups,alkene groups, aromatic groups, and the like.

The organosilicon compound, when used as an external electron donorserving as one component of a Ziegler-Natta catalyst system for olefinpolymerization, improves the ability of the catalyst system to produce apolymer (at least a portion of which is polyolefin) having acontrollable crystallinity while retaining high performance with respectto catalytic activity.

The organosilicon compound is used in the catalyst system in an amountthat the mole ratio of the organoaluminum compound to the organosiliconcompound is from about 2 to about 90. In another embodiment, the moleratio of the organoaluminum compound to the organosilicon compound isfrom about 5 to about 70. In yet another embodiment, the mole ration ofthe organoaluminum compound to the organosilicon compound is from about7 to about 35.

In one embodiment, the organosilicon compound is represented by chemicalformula (V):R_(n)Si(OR′)_(4-n)  (V)wherein each R and R′ independently represent a hydrocarbon group, and nis 0≦n<4.

Specific examples of the organosilicon compound of formula (V) include,but are not limited to, trimethylmethoxysilane, trimethylethoxysilane,dimethyldimethoxysilane, dimethyldiethoxysilane,diisopropyldimethoxysilane, diisobutyldimethoxysilane,t-butylmethyldimethoxysilane, t-butylmethyldiethoxysilane,t-amylmethyldiethoxysilane, dicyclopentyldimethoxysilane,diphenyldimethoxysilane, phenylmethyldimethoxysilane,diphenyldiethoxysilane, bis-o-tolydimethoxysilane,bis-m-tolydimethoxysilane, bis-p-tolydimethoxysilane,bis-p-tolydiethoxysilane, bisethylphenyldimethoxysilane,dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane,cyclohexylmethyldiethoxysilane, ethyltrimethoxysilane,ethyltriethoxysilane, vinyltrimethoxysilane, methyltrimethoxysilane,n-propyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane,phenyltrimethoxysilane, gamma-chloropropyltrimethoxysilane,methyltriethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane,t-butyltriethoxysilane, n-butyltriethoxysilane,iso-butyltriethoxysilane, phenyltriethoxysilane,gamma-amniopropyltriethoxysilane, cholotriethoxysilane,ethyltriisopropoxysilane, vinyltirbutoxysilane,cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane,2-norbornanetrimethoxysilane, 2-norbornanetriethoxysilane,2-norbornanemethyldimethoxysilane, ethyl silicate, butyl silicate,trimethylphenoxysilane, and methyltriallyloxysilane.

In another embodiment, the organosilicon compound is represented bychemical formula (VI):SiRR′_(m)(OR″)_(3-m)  (VI)

In the above formula (VI), 0≦m≦3, such as 0≦m≦2; and R independentlyrepresents a cyclic hydrocarbon or substituted cyclic hydrocarbon group.Specific examples of the group R include, but are not limited to,cyclopropyl; cyclobutyl; cyclopentyl; 2-methylcyclopentyl;3-methylcyclopentyl; 2-ethylcyclopentyl; 3-propylcyclopentyl;3-isopropylcyclopentyl; 3-butylcyclopentyl; 3-tetiary butyl cyclopentyl;2,2-dimethylcyclopentyl; 2,3-dimethylcyclopentyl;2,5-dimethylcyclopentyl; 2,2,5-trimethylcyclopentyl;2,3,4,5-tetramethylcyclopentyl; 2,2,5,5-tetramethylcyclopentyl;1-cyclopentylpropyl; 1-methyl-1-cyclopentylethyl; cyclopentenyl;2-cyclopentenyl; 3-cyclopentenyl; 2-methyl-1-cyclopentenyl;2-methyl-3-cyclopentenyl; 3-methyl-3-cyclopentenyl;2-ethyl-3-cyclopentenyl; 2,2-dimethyl-3-cyclopentenyl;2,5-dimethyl-3-cyclopentenyl; 2,3,4,5-tetramethyl-3-cyclopentenyl;2,2,5,5-tetramethyl-3-cyclopentenyl; 1,3-cyclopentadienyl;2,4-cyclopentadienyl; 1,4-cyclopentadienyl;2-methyl-1,3-cyclopentadienyl; 2-methyl-2,4-cyclopentadienyl;3-methyl-2,4-cyclopentadienyl; 2-ethyl-2,4-cyclopentadienyl;2,2-dimethyl-2,4-cyclopentadienyl; 2,3-dimethyl-2,4-cyclopentadienyl;2,5-dimethyl-2,4-cyclopentadienyl;2,3,4,5-tetramethyl-2,4-cyclopentadienyl; indenyl; 2-methylindenyl;2-ethylindenyl; 2-indenyl; 1-methyl-2-indenyl; 1,3-dimethyl-2-indenyl;indanyl; 2-methylindanyl; 2-indanyl; 1,3-dimethyl-2-indanyl;4,5,6,7-tetrahydroindenyl; 4,5,6,7-tetrahydro-2-indenyl;4,5,6,7-tetrahydro-1-methyl-2-indenyl;4,5,6,7-tetrahydro-1,3-dimethyl-2-indenyl; fluorenyl groups; cyclohexyl;methylcyclohexyls; ethylcylcohexyls; propylcyclohexyls;isopropylcyclohexyls; n-butylcyclohexyls; tertiary-butyl cyclohexyls;dimethylcyclohexyls; and trimethylcyclohexyls.

In formula (VI), R′ and R″ are identical or different and eachrepresents a hydrocarbons. Examples of R′ and R″ are alkyl, cycloalkyl,aryl and aralkyl groups having 3 or more carbon atoms. Furthermore, Rand R′ may be bridged by an alkyl group, etc. General examples oforganosilicon compounds are those of formula (VI) in which R iscyclopentyl group, R′ is an alkyl group such as methyl or cyclopentylgroup, and R″ is an alkyl group, particularly a methyl or ethyl group.

Specific examples of organosilicon compound of formula (VI) include, butare not limited to, trialkoxysilanes such ascyclopropyltrimethoxysilane, cyclobutyltrimethoxysilane,cyclopentyltrimethoxysilane, 2-methylcyclopentyltrimethoxysilane,2,3-dimethylcyclopentyltrimethoxysilane,2,5-dimethylcyclopentyltrimethoxysilane, cyclopentyltriethoxysilane,cyclopentenyltrimethoxysilane, 3-cyclopentenyltrimethoxysilane,2,4-cyclopentadienyltrimethoxysilane, indenyltrimethoxysilane andfluorenyltrimethoxysilane; dialkoxysilanes such asdicyclopentyldimethoxysilane, bis(2-methylcyclopentyl)dimethoxysilane,bis(3-tertiary butylcyclopentyl)dimethoxysilane,bis(2,3-dimethylcyclopentyl)dimethoxysilane,bis(2,5-dimethylcyclopentyl)dimethoxysilane,dicyclopentyldiethoxysilane, dicyclobutyldiethoxysilane,cyclopropylcyclobutyldiethoxysilane, dicyclopentenyldimethoxysilane,di(3-cyclopentenyl)dimethoxysilane,bis(2,5-dimethyl-3-cyclopentenyl)dimethoxysilane,di-2,4-cyclopentadienyl)dimethoxysilane,bis(2,5-dimethyl-2,4-cyclopentadienyl)dimethoxysilane,bis(1-methyl-1-cyclopentylethyl)dimethoxysilane,cyclopentylcyclopentenyldimethoxysilane,cyclopentylcyclopentadienyldimethoxysilane, diindenyldimethoxysilane,bis(1,3-dimethyl-2-indenyl)dimethoxysilane,cyclopentadienylindenyldimethoxysilane, difluorenyldimethoxysilane,cyclopentylfluorenyldimethoxysilane and indenylfluorenyldimethoxysilane;monoalkoxysilanes such as tricyclopentylmethoxysilane,tricyclopentenylmethoxysilane, tricyclopentadienylmethoxysilane,tricyclopentylethoxysilane, dicyclopentylmethylmethoxysilane,dicyclopentylethylmethoxysilane, dicyclopentylmethylethoxysilane,cyclopentyldimethylmethoxysilane, cyclopentyldiethylmethoxysilane,cyclopentyldimethylethoxysilane,bis(2,5-dimethylcyclopentyl)cyclopentylmethoxysilane,dicyclopentylcyclopentenylmethoxysilane,dicyclopentylcyclopentenadienylmethoxysilane anddiindenylcyclopentylmethoxysilane; andethylenebis-cyclopentyldimethoxysilane.

Polymerization of olefins in accordance with the presently disclosed andclaimed inventive concept(s) is carried out in the presence of thecatalyst system described above. Generally, olefins are contacted withthe catalyst system described above under suitable conditions to formdesired polymer products. In one embodiment, preliminary polymerizationdescribed below is carried out before main polymerization. In anotherembodiment, polymerization is carried out without preliminarypolymerization. In yet another embodiment, the formation of copolymer iscarried out using at least two polymerization zones.

In preliminary polymerization, the solid catalyst component is usuallyemployed in combination with at least a portion of the organoaluminumcompound. This process may be carried partially or completely in thepresence of the organosilicon compound (i.e. the external electron donorcompound). The concentration of the catalyst system used in thepreliminary polymerization reactor may be much higher than that in thereaction system of the main polymerization.

The concentration of the solid catalyst component in the preliminarypolymerization reactor is usually from about 0.01 to about 200millimoles, preferably from about 0.05 to about 100 millimoles,calculated as titanium atoms per liter of an inert hydrocarbon mediumdescribed below. In one embodiment, the preliminary polymerization iscarried out by adding an olefin and the above catalyst systemingredients to an inert hydrocarbon medium and polymerizing the olefinunder controllable conditions.

Specific examples of the inert hydrocarbon medium include, but are notlimited to, aliphatic hydrocarbons such as propane, butane, pentane,hexane, heptanes, octane, decane, dodecane and kerosene; alicyclichydrocarbons such as cyclopentane, cyclohexane and methylcyclopentane;and aromatic hydrocarbons such as benzene, toluene and xylene; andmixtures thereof. In the presently disclosed and claimed inventiveconcept(s), a liquid olefin may be used partially or completely as theinert hydrocarbon medium.

The reaction temperature for the preliminary polymerization issufficient for the resulting preliminary polymer to be substantiallyinsoluble in the inert hydrocarbon medium. In one embodiment, thetemperature is from about −20 degrees Celsius to about 100 degreesCelsius. In another embodiment, the temperature is from about −10degrees Celsius to about 80 degrees Celsius. In yet another embodiment,the temperature is from about 0 degrees Celsius to about 40 degreesCelsius.

Optionally, a molecular-weight controlling agent, such as hydrogen, maybe used in the preliminary polymerization. The molecular weightcontrolling agent is used in such an amount that the polymer obtained bythe preliminary polymerization has an intrinsic viscosity, measured indecalin at 135 degrees Celsius, of at least about 0.2 dl/g, andpreferably from about 0.5 to 10 dl/g.

In one embodiment, the preliminary polymerization is desirably carriedout so that from about 0.1 g to about 1,000 g of a polymer is formed pergram of the solid catalyst component of the catalyst system. In anotherembodiment, the preliminary polymerization is desirably carried out sothat from about 0.3 g to about 500 g of a polymer is formed per gram ofthe solid catalyst component. If the amount of the polymer formed by thepreliminary polymerization is too large, the efficiency of producing theolefin polymer in the main polymerization may sometimes decrease, andwhen the resulting olefin polymer is molded into a film or anotherarticle, “fish eyes” (i.e. granular dots or small circles in a moldedarticle of otherwise uniform and constant transparency) tend to occur inthe molded article. The preliminary polymerization may be carried outbatchwise or continuously.

After the preliminary polymerization is conducted as outlined above, oralternatively, without performing the preliminary polymerization, themain polymerization of an olefin feedstock is carried out in thepresence of the above-described olefin polymerization catalyst system,i.e. the catalyst system is formed from the solid catalyst component,the organoaluminum compound and the organosilicon compound (the externalelectron donor compound).

Examples of olefins that can be used in the main polymerization arealpha-olefins having 2 to 20 carbon atoms such as ethylene, propylene,1-butene, 4-methyl-1-pentene, 1-pentene, 1-octene, 1-hexene,3-methyl-1-pentene, 3-methyl-1-butene, 1-decene, 1-tetradecene,1-eicosene, and vinylcyclohexane. In the process of the presentlydisclosed and claimed inventive concept(s), these alpha-olefins may beused individually or in any combinations as will be apparent to one ofordinary skill in the art given the present disclosure.

In one embodiment, propylene or 1-butene is homopolymerized, or,alternatively, a mixed olefin containing propylene or 1-butene as a maincomponent is copolymerized. When a mixed olefin is selected or used, theproportion of propylene or 1-butene as the main component is usually atleast about 50 mole %, preferably at least about 70 mole %.

By performing the preliminary polymerization, the catalyst systemthereafter utilized in the main polymerization can be adjusted to selectdifferent degrees of activity. This adjustment tends to result in apowdery polymer having a high bulk density. Furthermore, when thepreliminary polymerization is carried out, the particles shape of theresulting polymer becomes spherical. In the case of slurrypolymerization, the slurry attains excellent characteristics, while inthe case of gas phase polymerization, the polymer seed bed attainsexcellent characteristics. Each type of polymerization is preceded bythe preliminary polymerization as described herein. Furthermore, inthese embodiments, a polymer having a high stereoregularity index can beproduced with a high catalytic efficiency by polymerizing analpha-olefin having at least 3 carbon atoms. Accordingly, when producingthe propylene copolymer, the resulting copolymer powder or the copolymerbecomes easy to process.

In the homopolymerization of these olefins, a polyunsaturated compoundsuch as conjugated diene or non-conjugated diene may be used as acomonomer. Examples of comonomers include styrene, butadiene,acrylonitrile, acrylamide, alpha-methyl styrene, chlorostyrene, vinyltoluene, divinyl benzene, diallyphthalate, alkyl methacrylates and alkylacrylates. In one embodiment, the comonomers include thermoplastic andelastomeric monomers.

The main polymerization of an olefin is typically carried out in thegaseous or liquid phase. In one embodiment, the main polymerizationemploys a catalyst system containing the solid catalyst component in anamount from about 0.001 to about 0.75 millimoles calculated as Ti atomper liter of the volume of the polymerization zone, the organoaluminumcompound in an amount from about 1 to about 2,000 moles per mole oftitanium atoms in the solid catalyst component, and the organosiliconcompound in an amount from about 0.001 to about 10 moles calculated asSi atoms in the organosilicon compound per mole of the metal atoms inthe organoaluminum compound.

In another embodiment, the main polymerization employs a catalyst systemcontaining the solid catalyst component in an amount of from 0.005 toabout 0.5 milimoles calculated as Ti atom per liter of the volume of thepolymerization zone, the organoaluminum compound in an amount from about5 to about 500 moles per mole of titanium atoms in the solid catalystcomponent, and the organosilicon compound in an amount from about 0.01to about 2 moles calculated as Si atoms in the organosilicon compoundper mole of the metal atoms in the organoaluminum compound. In yetanother embodiment, the main polymerization employs a catalyst systemcontaining the alkyl benzoate derivative in an amount from about 0.005to about 1 mole calculated as Si atoms in the organosilicon compound permole of the metal atoms in the organoaluminum compound.

When the organoaluminum compound and the organosilicon compound are usedpartially in the preliminary polymerization, the catalyst systemsubjected to the preliminary polymerization is used together with theremainder of the catalyst system components. The catalyst systemsubjected to the preliminary polymerization may contain the product ofthe preliminary polymerization.

The use of hydrogen at the time of polymerization promotes andcontributes to control of the molecular weight of the resulting polymer,and the polymer obtained may have a desirable melt flow rate. Thestereoregularity index of the resulting polymer and the activity of thecatalyst system are thereby increased when the methods and systems ofthe presently disclosed and claimed inventive concept(s) are utilized.

In one embodiment, the polymerization temperature in the mainpolymerization is from about 20 degree Celsius to about 200 degreesCelsius. In another embodiment, the polymerization temperature in themain polymerization is from about 50 degree Celsius to about 180 degreesCelsius. In one embodiment, the polymerization pressure in the mainpolymerization is typically from atmospheric pressure to about 100kg/cm². In another embodiment, the polymerization pressure in the mainpolymerization is typically from about 2 kg/cm² to about 50 kg/cm². Themain polymerization may be carried out batchwise, semi-continuously orcontinuously. The main polymerization may also be carried out in two ormore stages under different reaction conditions.

The olefin polymer so obtained may be a homopolymer, a random copolymer,a block copolymer or an impact copolymer. The impact copolymer containsan intimate mixture of a polyolefin homopolymer and a polyolefin rubber.Examples of polyolefin rubbers include ethylene propylene rubber (EPR)such as ethylene propylene methylene copolymer rubber (EPM) and ethylenepropylene diene methylene terpolymer rubber (EPDM).

The olefin polymer obtained by using the catalyst system has a verysmall amount of an amorphous polymer component and therefore a smallamount of a hydrocarbon-soluble component. Accordingly, a film moldedfrom the resultant polymer has low surface tackiness.

The polyolefin obtained by the polymerization process is excellent inparticle size distribution, particle diameter and bulk density, and thecopolyolefin obtained has a narrow composition distribution. In animpact copolymer, excellent fluidity, low temperature resistance, and adesired balance between stiffness and elasticity can be obtained.

In one embodiment, propylene and an alpha-olefin having 2 or from about4 to about 20 carbon atoms are copolymerized in the presence of thecatalyst system described above. The catalyst system may be onesubjected to the preliminary polymerization described above. In anotherembodiment, propylene and an ethylene rubber are formed in two reactorscoupled in series to form an impact polymer.

The alpha-olefin having 2 carbon atoms is ethylene, and examples of thealpha-olefin having about 4 to about 20 carbon atoms are 1-butene,1-pentene, 4-methyl-1-pentene, 1-octene, 1-hexene, 3-methyl-1-pentene,3-methyl-1-butene, 1-decene, vinylcyclohexane, 1-tetradecene, and thelike.

In the main polymerization, propylene may be copolymerized with two ormore such alpha-olefins. For example, it is possible to copolymerizepropylene with ethylene and 1-butene. In one embodiment, propylene iscopolymerized with ethylene, 1-butene or ethylene and 1-butene.

Block copolymerization of propylene and another alpha-olefin may becarried out in two stages. The polymerization in a first stage may bethe homopolymerization of propylene or the copolymerization of propylenewith the other alpha-olefin. In one embodiment, the amount of themonomers polymerized in the first stage is from about 50 to about 95% byweight. In another embodiment, the amount of the monomers polymerized inthe first stage is from about 60 to about 90% by weight. In thepresently disclosed and claimed inventive concept(s), this first stagepolymerization may, as required be carried out in two or more stagesunder the same or different polymerization conditions.

In one embodiment, the polymerization in a second stage is desirablycarried out such that the mole ratio of propylene to the otheralpha-olefin(s) is from about 10/90 to about 90/10. In anotherembodiment, the polymerization in a second stage is desirably carriedout such that the mole ratio of propylene to the other alpha-olefin(s)is from about 20/80 to about 80/20. In yet another embodiment, thepolymerization in a second stage is desirably carried out such that themole ratio of propylene to the other alpha-olefin(s) is from about 30/70to about 70/30. Producing a crystalline polymer or copolymer of anotheralpha-olefin may be provided in the second polymerization stage.

The propylene copolymer so obtained may be a random copolymer or theabove-described block copolymer. This propylene copolymer typicallycontains from about 7 to about 50 mole % of units derived from thealpha-olefin having 2 or from about 4 to about 20 carbon atoms. In oneembodiment, a propylene random copolymer contains from about 7 to about20 mole % of units derived from the alpha-olefin having 2 or from about4 to about 20 carbon atoms. In another embodiment, the propylene blockcopolymer contains from about 10 to about 50 mole % of units derivedfrom the alpha-olefin having 2 or 4-20 carbon atoms.

In another embodiment, copolymers made with the catalyst system containfrom about 50% to about 99% by weight poly-alpha-olefins and from about1% to about 50% by weight comonomers (such as thermoplastic orelastomeric monomers). In another embodiment, copolymers made with thecatalyst system contain from about 75% to about 98% by weightpoly-alpha-olefins and from about 2% to about 25% by weight comonomers.

It should be understood that where there is no reference to a particularpolyunsaturated compound, the method of polymerization, the amount ofthe catalyst system and the polymerization conditions, the samedescription as any of the above embodiments are applicable and would beapparent for one of ordinary skill in the art.

The catalysts/methods of the presently disclosed and claimed inventiveconcept(s) can, in some embodiments, produce poly-alpha-olefins havingxylene soluble (XS) from about 0.5% to about 10%. In another embodiment,poly-alpha-olefins having xylene soluble (XS) from about 1.5% to about8% are produced in accordance with the presently disclosed and claimedinventive concept(s). XS refers to the percent of solid polymer thatdissolves into xylene. A low XS % value generally corresponds to ahighly isotactic polymer (i.e. higher crystallinity), whereas a high XS% value generally corresponds to a low isotactic polymer.

In one embodiment, the catalyst efficiency (measured as kilogram ofpolymer produced per gram of catalyst) of the catalyst system of thepresently disclosed and claimed inventive concept(s) is at least about20. In another embodiment, the catalyst efficiency of the catalystsystem of the presently disclosed and claimed inventive concept(s) is atleast about 40.

The catalysts/methods of the presently disclosed and claimed inventiveconcept(s) can in some instances lead to the production ofpoly-alpha-olefins having melt flow indexes (MFI) from about 0.1 toabout 100. The MFI is measured according to ASTM standard D1238. Inanother embodiment, poly-alpha-olefins having an MFI from about 5 toabout 30 are produced in accordance with the presently disclosed andclaimed inventive concept(s). In one embodiment, an impactpolypropylene-ethylenepropylene rubber product has an MFI from about 4to about 10. In another embodiment, an impactpolypropylene-ethylenepropylene rubber product has an MFI from about 5to about 9. In some instances a relatively high MFI indicates relativelyhigh catalyst efficiency is obtainable.

The catalysts/methods of the presently disclosed and claimed inventiveconcept(s) can in some instances lead to the production ofpoly-alpha-olefins having bulk densities (BD) of at least about 0.3cc/g. In another embodiment, poly-alpha-olefins having a BD of at leastabout 0.4 cc/g are produced in accordance with the presently disclosedand claimed inventive concept(s).

In one embodiment, an impact polypropylene-ethylenepropylene rubberproduct having a BD of at least about 0.3 cc/g is produced in accordancewith the presently disclosed and claimed inventive concept(s). Inanother embodiment, an impact polypropylene-ethylenepropylene rubberproduct having a BD of at least about 0.4 cc/g is produced in accordancewith the presently disclosed and claimed inventive concept(s).

The catalysts/methods of the presently disclosed and claimed inventiveconcept(s) lead to the production of poly-alpha-olefins having arelatively narrow molecular weight distribution. Polydispersive Index(PI) is strictly connected with the molecular weight distribution of thepolymer. PI is calculated as the weight average molecular weight dividedby the number average molecular weight, PI=M_(w)/M_(n). In oneembodiment, the PI of a polypropylene polymer made with the catalystsystem is from about 2 to about 8. In another embodiment, the PI of apolypropylene polymer made with the catalyst system is from about 3 toabout 5.

The presently disclosed and claimed inventive concept(s) can lead to theproduction of a propylene block copolymer and impact copolymersincluding polypropylene based impact copolymer having one or moreexcellent melt-flowability, moldability desirable balance betweenrigidity and elasticity, good stereospecific control, good control overpolymer particle size, shape, size distribution, and molecular weightdistribution, and impact strength with a high catalytic efficiencyand/or good operability. Employing the catalyst systems containing thesolid catalyst component according to the presently disclosed andclaimed inventive concept(s) yields catalysts simultaneously having highcatalytic efficiency, and one or more of excellent melt-flowability,extrudability, moldability, rigidity-elasticity and impact strength.

Examples of systems for polymerizing olefins are now described.Referring to FIG. 1, a high level schematic diagram of a system 10 forpolymerizing olefins is shown. Inlet 12 is used to introduce into areactor 14 catalyst system components, olefins, optional comonomers,hydrogen gas, fluid media, pH adjusters, surfactants, and any otheradditives. Although only one inlet is shown, many often are employed.Reactor 14 is any suitable vehicle that can polymerize olefins. Examplesof reactor 14 include a single reactor, a series of two or morereactors, slurry reactors, fixed bed reactors, gas phase reactors,fluidized gas reactors, loop reactors, multizone circulating reactors,and the like. Once polymerization is complete, or as polyolefins areproduced, the polymer product is removed from the reactor 14 via outlet16 which leads to a collector 18. Collector 18 may include downstreamprocessing, such as heating, extrusion, molding, and the like.

Referring to FIG. 2, a schematic diagram of a multizone circulatingreactor 20 that can be employed as the reactor 14 in FIG. 1 or thereactor 44 in FIG. 3 for making polyolefins is shown. The multizonecirculating reactor 20 substitutes a series of separate reactors with asingle reactor loop that permits different gas phase polymerizationconditions in two sides due to use of a liquid barrier. In the multizonecirculating reactor 20, a first zone starts out rich in olefin monomers,and optionally one or more comonomers. A second zone is rich in hydrogengas, and a high velocity gas flow divides the growing resin particlesout loosely. The two zones produce resins of different molecular weightsand/or monomer compositions. Polymer granules grow as they circulatearound the loop, building up alternating layers of each polymer fractionin an onion like fashion. Each polymer particle constitutes an intimatecombination of both polymer fractions.

In operation, the polymer particles pass up through the fluidizing gasin an ascending side 24 of the loop and come down through the liquidmonomer on a descending side 26. The same or different monomers (andagain optionally one or more comonomers) can be added in the two reactorlegs. The reactor uses the catalyst system described above.

In the liquid/gas separation zone 30, hydrogen gas is removed to cooland recirculate. Polymer granules are then packed into the top of thedescending side 26, where they then descend. Monomers are introduced asliquids in this section. Conditions in the top of the descending side 26can be varied with different combinations and/or proportions of monomersin successive passes.

Referring to FIG. 3, a high level schematic diagram of another system 40for polymerizing olefins is shown. This system is ideally suited to makeimpact polymers. A reactor 44, such as a single reactor, a series ofreactors, or a multizone circulating reactor is paired with a gas phaseor a fluidized bed reactor 48 downstream containing the catalyst systemsdescribed above to make impact copolymers with desirable impact tostiffness balance or greater softness than made with conventionalcatalyst systems. Inlet 42 is used to introduce into the reactor 44catalyst system components, olefins, optional comonomers, hydrogen gas,fluid media, pH adjusters, surfactants, and any other additives.Although only one inlet is shown, many often are employed. Throughtransfer means 46 the polyolefin made in the first reactor 44 is sent toa second reactor 48. Feed 50 is used to introduce catalyst systemcomponents, olefins, optional comonomers, fluid media, and any otheradditives. The second reactor 48 may or may not contain catalyst systemcomponents. Again, although only one inlet is shown, many often areemployed. Once the second polymerization is complete, or as impactcopolymers are produced, the polymer product is removed from the secondreactor 48 via outlet 52 which leads to a collector 54. Collector 54 mayinclude downstream processing, such as heating, extrusion, molding, andthe like. At least one of the first reactor 44 and the second reactor 48contains catalyst systems in accordance with the invention.

When making an impact copolymer, polypropylene can be formed in thefirst reactor while an ethylene propylene rubber can be formed in thesecond reactor. In this polymerization, the ethylene propylene rubber inthe second reactor is formed with the matrix (and particularly withinthe pores) of the polypropylene formed in the first reactor.Consequently, an intimate mixture of an impact copolymer is formed,wherein the polymer product appears as a single polymer product. Such anintimate mixture cannot be made by simply mixing a polypropylene productwith an ethylene propylene rubber product.

Although not shown in any of the figures, the systems and reactors canbe controlled, optionally with feedback based on continuous orintermittent testing, using a processor equipped with an optional memoryand controllers. For example, a processor may be connected to one ormore of the reactors, inlets, outlets, testing/measuring systems coupledwith the reactors, and the like to monitor and/or control thepolymerization process, based on preset data concerning the reactions,and/or based on testing/measuring data generated during a reaction. Thecontroller may control valves, flow rates, the amounts of materialsentering the systems, the conditions (temperature, reaction time, pH,etc.) of the reactions, and the like, as instructed by the processor.The processor may contain or be coupled to a memory that contains dataconcerning various aspects of the polymerization process.

With respect to any figure or numerical range for a givencharacteristic, a figure or a parameter from one range may be combinedwith another figure or a parameter from a different range for the samecharacteristic to generate a numerical range.

Other than in the operating examples, or where otherwise indicated, allnumbers, values and/or expressions referring to quantities ofingredients, reaction conditions, etc., used in the specification andclaims are to be understood as modified in all instances by the term“about.”

The following examples illustrate the presently disclosed and claimedinventive concept(s). Unless otherwise indicated in the followingexamples and elsewhere in the specification and claims, all parts andpercentages are by weight, all temperatures are in degrees Celsius, andpressure is at or near atmospheric pressure.

Example 1

Into a 250 ml Buchi reactor under N₂ a mixture of 3.3 g MgCl₂, 0.8 gphthalic anhydride, 50.92 g toluene, 6.41 g epichlorohydrin, and 6.70 gtributylphosphate was added. The mixture was heated for two hours whileagitating at 400 rpm and 60° C. The reaction mixture was then cooled to−30° C. and 37.75 ml of TiCl₄ was added slowly while the reactortemperature was maintained below −26° C. After the addition theagitation rate was reduced to 200 rpm and the temperature was rampedfrom −26° C. to 0° C. in one hour then from 0° C. to 85° C. in one hour.

The mixture was held at 85° C. for 30 minutes and then 0.8 g of1-ethyl-2-methoxy ethyl 4-methylbenzoate was added (mother liquoraddition). The mixture was stirred at 85° C. for one hour and thenfiltered. The solids were re-suspended in 38 ml of toluene and 0.3 g of1-ethyl-2-methoxy ethyl 4-methylbenzoate was added to the reactor(toluene addition). The mixture was agitated for one hour at 85° C. and200 rpm. After filtered and washed twice with 65 ml toluene the mixturewas left over night in toluene under N₂.

After filtering off the toluene 66.25 ml of 10-vol % TiCl₄ was addedinto toluene then heated to and held at 95° C. with 400 rpm agitationfor one hour (1^(st) activation). The solids were filtered thenre-suspended in 66.25 ml of 10-vo % TiCl₄ in toluene. The mixture washeld at 110° C. for thirty minutes after the solids were once againfiltered. The step was repeated two more times. The final catalyst waswashed four times with 65 ml of hexane then discharged from the reactorin hexane.

Propylene polymerization was performed in a 3.4 liter reactor. Thereactor was purged at 100° C. under nitrogen for one hour. At roomtemperature, 1.5 ml of 25-wt % triethylaluminum (TEAL) in heptane wasadded into the reactor. Then 1.0 ml of 0.0768 M solution of cyclohexylmethyl dimethoxy silane followed by 1 ml of 1-wt % catalyst slurry wasadded into the reactor. The reactor was pressurized with H₂ to 3.5 psigthen charged with 1500 ml propylene. The reactor was heated to then heldat 70° C. for one hour. At the end of the hold, the reactor was ventedand the polymer was recovered. Yields: 288 g polypropylene. Catalystactivity: 37.3 kg/g. Xylene soluble: 4.7%. MFR: 4.7 dg/minPolydispersity index (PI): 3.6.

Example 2

The catalyst was synthesized under the same conditions as Example 1except 0.8 g of 1-ethyl-2-methoxy ethyl 4-methylbenzoate was added intothe mother liquor addition stage and 0.3 g of 1-ethyl-2-methoxy ethyl4-methylbenzoate was added into the 1^(st) activation stage.

Propylene polymerization was performed under the same conditions asExample 1. Yield: 261 g polypropylene. Catalyst activity: 26.1 kg/g.Xylene soluble: 4.8%. MFR: 5.7 dg/min. PI: 3.8.

Example 3

The catalyst was synthesized under the same conditions as Example 1except 0.4 g of 1-ethyl-2-methoxy ethyl 4-methylbenzoate was added inthe mother liquor addition. 0.8 g of 1-ethyl-2-methoxy ethyl4-methylbenzoate was added into the mother liquor addition stage and 0.3g of 1-methoxybutan-2-yl 4-methylbenzoate was added into the 1^(st)activation stage.

Propylene polymerization was performed under the same conditions asExample 1. Yield: 327 g polypropylene. Catalyst activity: 32.7 kg/g.Xylene soluble: 3.8%. MFR: 4.6 dg/min. PI: 3.6

Example 4

The catalyst was synthesized under the same conditions as Example 1except 0.8 g of 1-ethyl-2-methoxy ethyl 4-methylbenzoate was added intothe mother liquor addition stage. 0.3 g of 1-ethyl-2-methoxy ethyl4-methylbenzoate was added into the toluene cook and 0.3 g of1-ethyl-2-methoxy ethyl 4-methylbenzoate was added into the 1^(st)activation stage.

Propylene polymerization was performed under the same conditions asExample 1. Yield: 300 g polypropylene. Catalyst activity: 30.0 kg/g.Xylene soluble: 4.3%. MFR: 2.9 dg/min. PI: 3.8.

Example 5

The catalyst was synthesized under the same conditions as Example 1except 1.3 g of 1-ethyl-2-methoxy ethyl 4-methylbenzoate was added intothe mother liquor addition stage.

Propylene polymerization was performed under the same conditions asExample 1. Yield: 360 g polypropylene. Catalyst activity: 36.0 kg/g.Xylene soluble: 5.9%. MFR: 4.2 dg/min. PI: 3.6.

Example 6

The catalyst was synthesized under the same conditions as Example 1except 0.95 g of 1-t-butyl-2-methoxy ethyl 4-methylbenzoate was addedinto the mother liquor addition stage and 0.35 g of 1-t-butyl-2-methoxyethyl 4-methylbenzoate was added into the toluene cook.

Propylene polymerization was performed under the same conditions asExample 1. Yield: 270 g polypropylene. Catalyst activity: 27.0 kg/g.Xylene soluble: 6.6%. MFR: 5.0 dg/min. PI: 4.1.

Example 7

The catalyst was synthesized under the same conditions as Example 1except 1.06 g of 1-isononyl-2-methoxy ethyl 4-methylbenzoate was addedinto the mother liquor addition stage and 0.47 g of 1-isononyl-2-methoxyethyl 4-methylbenzoate was added into the toluene cook.

Propylene polymerization was performed under the same conditions asExample 1. Yield: 356 g polypropylene. Catalyst activity: 35.6 kg/g.Xylene soluble: 3.1%. MFR: 5.2 dg/min. PI: 4.0.

Example 8

The catalyst was synthesized under the same conditions as Example 1except 1.16 g of 1-octyl-2-methoxy ethyl 4-methylbenzoate was added intothe mother liquor addition stage and 0.51 g of 1-octyl-2-methoxy ethyl4-methylbenzoate was added into the toluene cook.

Propylene polymerization was performed under the same conditions asExample 1. Yield: 335 g polypropylene. Catalyst activity: 33.5 kg/g.Xylene soluble: 4.5%. MFR: 4.3 dg/min. PI: 4.2.

Example 9

The catalyst was synthesized under the same conditions as Example 1except 0.95 g of 1-butyl-2-methoxy ethyl 4-methylbenzoate was added intothe mother liquor addition stage and 0.42 g of 1-butyl-2-methoxy ethyl4-methylbenzoate was added into the toluene cook.

Propylene polymerization was performed under the same conditions asExample 1. Yield: 392 g polypropylene. Catalyst activity: 39.2 kg/g.Xylene soluble: 4.3%. MFR: 3.7 dg/min. PI: 4.1.

Example 10

The catalyst was synthesized under the same conditions as Example 1except 1.26 g of 1-butyl-2-methoxy ethyl 2-methylbenzoate was added intothe mother liquor addition stage.

Propylene polymerization was performed under the same conditions asExample 1. Yield: 221 g polypropylene. Catalyst activity: 22.1 kg/g.Xylene soluble: 5.2%. MFR: 14.6 dg/min.

Example 11

The catalyst was synthesized under the same conditions as Example 1except 1.47 g of 1-hexyl-2-methoxy ethyl 2-methylbenzoate was added intothe mother liquor addition stage.

Propylene polymerization was performed under the same conditions asExample 1. Yield: 233 g polypropylene. Catalyst activity: 23.3 kg/g.Xylene soluble: 5.2%. MFR: 17.4 dg/min.

It is, of course, not possible to describe every conceivable combinationof the components or methodologies for purpose of describing thedisclosed information, but one of ordinary skill in the art canrecognize that many further combinations and permutations of thedisclosed information are possible. Accordingly, the disclosedinformation is intended to embrace all such alternations, modificationsand variations that fall within the spirit and scope of the appendedclaims. Furthermore, to the extent that the term “includes,” “has,”“involve,” or variants thereof is used in either the detaileddescription or the claims, such term is intended to be inclusive in amanner similar to the term “comprising” as “comprising” is interpretedwhen employed as a transitional word in a claim.

What is claimed is:
 1. A solid catalyst component for use in olefinicpolymerization, comprising: a compound containing titanium, a compoundcontaining magnesium, a compound containing halogen and an internalelectron donor compound, wherein the internal electron donor compoundcomprises at least one 1-alkyl-2-methoxy ethyl 4-alkylbenzoate selectedfrom the group consisting of 1-ethyl-2-methoxy ethyl 4-methylbenzoate,1-ethyl-2-methoxy ethyl 4-ethylbenzoate, 1-ethyl-2-methoxy ethyl4-propylbenzoate, 1-ethyl-2-methoxy ethyl 4-butylbenzoate,1-propyl-2-methoxy ethyl 4-methylbenzoate, 1-propyl-2-methoxy ethyl4-ethylbenzoate, 1-propyl-2-methoxy ethyl 4-propylbenzoate,1-propyl-2-methoxy ethyl 4-butylbenzoate, 1-isopropyl-2-methoxy ethyl4-methylbenzoate, 1-isopropyl-2-methoxy ethyl 4-ethylbenzoate,1-isopropyl-2-methoxy ethyl 4-propyllbenzoate, 1-isopropyl-2-methoxyethyl 4-butylbenzoate, 1-t-butyl-2-methoxy ethyl 4-methylbenzoate,1-t-butyl-2-methoxy ethyl 4-ethylbenzoate, 1-t-butyl-2-methoxy ethyl4-propylbenzoate, 1-t-butyl-2-methoxy ethyl 4-butylbenzoate,1-isobutyl-2-methoxy ethyl 4-methylbenzoate, 1-isobutyl-2-methoxy ethyl4-ethylbenzoate, 1-isobutyl-2-methoxy ethyl 4-propylbenzoate,1-isobutyl-2-methoxy ethyl 4-butylbenzoate, 1-n-butyl-2-methoxy ethyl4-methylbenzoate, 1-n-butyl-2-methoxy ethyl 4-ethylbenzoate,1-n-butyl-2-methoxy ethyl 4-propylbenzoate, 1-n-butyl-2-methoxy ethyl4-butylbenzoate, 1-n-pentyl-2-methoxy ethyl 4-methylbenzoate,1-n-pentyl-2-methoxy ethyl 4-ethylbenzoate, 1-n-pentyl-2-methoxy ethyl4-propylbenzoate, 1-n-pentyl-2-methoxy ethyl 4-butylbenzoate,1-isopentyl-2-methoxy ethyl 4-methylbenzoate, 1-isopentyl-2-methoxyethyl 4-ethylbenzoate, 1-isopentyl-2-methoxy ethyl 4-propylbenzoate,1-isopentyl-2-methoxy ethyl 4-butylbenzoate, 1-n-hexyl-2-methoxy ethyl4-methylbenzoate, 1-n-hexyl-2-methoxy ethyl 4-ethylbenzoate,1-n-hexyl-2-methoxy ethyl 4-propylbenzoate, 1-n-hexyl-2-methoxy ethyl4-butylbenzoate, 1-isohexyl-2-methoxy ethyl 4-methylbenzoate,1-isohexyl-2-methoxy ethyl 4-ethylbenzoate, 1-isohexyl-2-methoxy ethyl4-propylbenzoate, 1-isohexyl-2-methoxy ethyl 4-butylbenzoate,1-n-heptyl-2-methoxy ethyl 4-methylbenzoate, 1-n-heptyl-2-methoxy ethyl4-ethylbenzoate, 1-n-heptyl-2-methoxy ethyl 4-propylbenzoate,1-n-heptyl-2-methoxy ethyl 4-butylbenzoate, 1-isoheptyl-2-methoxy ethyl4-methylbenzoate, 1-isoheptyl-2-methoxy ethyl 4-ethylbenzoate,1-isoheptyl-2-methoxy ethyl 4-propylbenzoate, 1-isoheptyl-2-methoxyethyl 4-butylbenzoate, 1-n-octyl-2-methoxy ethyl 4-methylbenzoate,1-n-octyl-2-methoxy ethyl 4-ethylbenzoate, 1-n-octyl-2-methoxy ethyl4-propylbenzoate, 1-n-octyl-2-methoxy ethyl 4-butylbenzoate,1-isooctyl-2-methoxy ethyl 4-methylbenzoate, 1-isooctyl-2-methoxy ethyl4-ethylbenzoate, 1-isooctyl-2-methoxy ethyl 4-propylbenzoate,1-isooctyl-2-methoxy ethyl 4-butylbenzoate, 1-nonyl-2-methoxy ethyl4-methylbenzoate, 1-nonyl-2-methoxy ethyl 4-ethylbenzoate,1-nonyl-2-methoxy ethyl 4-propylbenzoate, 1-nonyl-2-methoxy ethyl4-butylbenzoate, 1-i-nonyl-2-methoxy ethyl 4-methylbenzoate,1-i-nonyl-2-methoxy ethyl 4-ethylbenzoate, 1-i-nonyl-2-methoxy ethyl4-propylbenzoate, and 1-i-nonyl-2-methoxy ethyl 4-butylbenzoate.